Catalyst for fluid catalytic cracking of heavy hydrocarbon oil and method of fluid catalytic cracking

ABSTRACT

The present invention provides an FCC catalyst which not only deactivates catalyst poison metals, such as nickel, vanadium and the like, in feedstock oils, inhibits the generation of hydrogen or coke, has excellent cracking activity and bottom oil-treating ability, and can yield a gasoline and LCO fraction in high yields, but also retains the performances on a high level over long and has an improved catalyst life; and an FCC method using the catalyst.  
     The present invention relates to an FCC catalyst which comprises a compound of a bivalent metal or of bivalent and trivalent metals showing an XRD pattern of a carbonate of the bivalent metal; an inorganic oxide matrix and the compound dispersed therein; or an inorganic oxide matrix and the compound dispersed therein together with a crystalline aluminosilicate zeolite, and relates to an FCC method in which at least one of the catalysts are used in combination with an FCC catalyst obtained by evenly dispersing a crystalline aluminosilicate zeolite in an inorganic oxide matrix.

TECHNICAL FIELD

[0001] The present invention relates to a catalyst for fluidizedcatalytic cracking (hereinafter sometimes referred to as “FCC”) of aheavy hydrocarbon oil and a method of FCC of the oil with the catalyst.More particularly, the present invention relates to a highly durable FCCcatalyst which not only deactivates catalyst poison metals contained inthe oil, e.g., nickel and vanadium, is reduced in the amount of hydrogenor coke yielded, has excellent cracking activity and bottom oil-treatingability, and can yield a gasoline and an LCO fraction in high yieldswithout lowering the octane number, but also can retain theseperformances on a high level over long, and relates to an FCC methodusing the catalyst.

BACKGROUND ART

[0002] Recently, in the catalytic cracking of hydrocarbon oils, there isa desire to upgrade a less expensive feedstock hydrocarbon oil of lowerquality, while there is an increasingly growing tendency for feedstockhydrocarbon oils to become heavier.

[0003] Heavy feedstock hydrocarbon oils contain a large amount of metalssuch as nickel, vanadium and the like, and the metals almost whollydeposit on the catalyst.

[0004] In particular, it is known that when vanadium deposits andaccumulates on the catalyst, it destroys the crystal structure of thecrystalline aluminosilicate zeolite which is an active ingredient of thecatalyst and therefore a considerable decrease in catalytic activity isbrought out and the amount of hydrogen and coke yielded is increased.

[0005] On the other hand, it is known that nickel causes catalyticdehydrogenation upon deposition and accumulation on the catalyst surfaceand therefore increase the amount of hydrogen and coke yielded isincreased and, as a result, nickel causes problems, for example, thatthe regeneration tower temperature is elevated.

[0006] When a feedstock hydrocarbon oil containing a large amount of aheavy bottom oil (e.g., topping residue or vacuum distillation residue)is used, not only the influences of the metals become greater but alsothe sulfur compounds contained in the bottom oil cause a problem thatthe amount of SO_(x) in the flue gas from a catalyst regeneration towerincreases and a product oil fraction, in particular a gasoline, has anincreased sulfur concentration.

[0007] Furthermore, increase of the treated amount of bottom oils leadsto an increase in catalyst makeup amount and causes problems relating toincrease in catalyst cost and load imposed on the environment due to anincrease in the amount of waste catalysts.

[0008] Up to now, in order to deactivate poison metals such as vanadiumor the like to be deposited on a catalyst to thereby improve the metalresistance of the catalyst, various techniques which incorporate a basiccompound or the like as a metal deactivator into the catalyst have beenproposed. Examples include a technique in which a water-soluble compoundof an alkaline earth metal or the like is ion-exchanged with a zeoliteor inorganic oxide matrix and a technique in which a water-insolubleoxide (e.g., dolomite, sepiolite, anion clay, or the like) isincorporated into an inorganic oxide matrix (JP-A-62-57652,JP-A-63-182031, JP-A-3-293039, etc.).

[0009] Although the compounds of alkaline earth metals have the effectof deactivating poison metals, they have no cracking ability when usedalone. Consequently, they are used after having been incorporated as ametal deactivator into an inorganic oxide matrix having a crackingability, as described above. However, in the catalyst, since thealkaline earth metal (especially a magnesium compound or the like) movesin the form of a low-melting compound during catalytic crackingreactions and the basic nature thereof destroys the crystal structure ofthe crystalline aluminosilicate zeolite, the thermal stability isreduced.

[0010] The catalyst described above obtained by incorporating a compoundof an alkaline earth metal into a crystalline aluminosilicate zeolitethrough ion exchange has problems, for example, that the gasolineproduct obtained through catalytic cracking reactions has a reducedoctane number (RON).

[0011] Furthermore, when anion clay or the like is used, the claynaturally occurring is rare and hence highly raises the catalyst cost,while synthetic products of the clay also are not inexpensive, resultingalso in an increased catalyst cost.

[0012] In addition, when a compound of an alkaline earth metal isdispersed as a metal deactivator in an inorganic oxide matrix, the pH ofthe catalyst slurry fluctuates considerably due to the basic nature ofthe compound so that it is difficult to produced the catalyst.

[0013] In particular, magnesium compounds dissolve away in the step ofcatalyst washing with ammonia, an aqueous ammonium sulfate solution orthe like (removal of an alkali metal such as sodium or potassium fromthe catalyst). It is hence difficult to wash catalysts containingmagnesium, and the incorporation thereof into catalysts is problematic.

[0014] On the other hand, an additional advantage of the catalystcompositions described above having the effect of trapping vanadium isthat they have SO_(x)-binding ability (see U.S. Pat. No. 4,889,615,etc.). The ability is effective in diminishing SO_(x) in the dischargegas from a regeneration tower and reducing the sulfur content of aproduct oil.

[0015] Heavy hydrocarbon oils, in particular, have a high sulfurcontent, and the sulfur compounds deposit on the catalyst together withcoke and become SO_(x) in the regeneration tower of the FCC apparatus.SO_(x) reacts with the basic metal oxide and is thus trapped in thecatalyst. The sulfur thus trapped can be separated and recovered afterit is converted to hydrogen sulfide through reactions in the riser. Itis known that the catalyst compositions thus diminish SO_(x) in thecombustion gas and reduce the sulfur content in the product oil.

[0016] However, when nickel accumulates on the catalyst surface, thereare often cases where the metal deactivator described above nodeactivating effect on the nickel. Accordingly, a technique of feeding aspecific antimony compound (organoantimony, etc.) to a feedstockhydrocarbon oil to thereby deactivate the nickel deposited on thecatalyst surface has been proposed (JP-A-63-63688, JP-A-1-213399, etc.).

[0017] However, the antimony compound accumulates as a metallic antimonydeposit (low-melting compound having a melting point of from 500 to 700°C.) on the control valve and the like in the FCC apparatus.

DISCLOSURE OF THE INVENTION

[0018] In view of the various points described above, an object of thepresent invention is to provide an FCC catalyst of the highly durabletype (having a life at least twice higher than the life of standardcatalysts) into which a metal deactivator can be incorporated withoutlowering the catalytic activity and which not only efficientlydeactivates catalyst poison metals contained in heavy feedstockhydrocarbons contained in feedstock oils, is reduced in the amount ofhydrogen or coke yielded, has excellent cracking activity and bottomoil-treating ability, and can yield a gasoline and an LCO fraction inhigh yields without lowering the octane number, but also can retainthese performances on a high level over long.

[0019] The present inventors made intensive investigations in order toaccomplish the object. As a result, it has been found that when aspecific carbonate selected from crystalline metal carbonates comprisinga bivalent metal and crystalline metal carbonates comprising a bivalentmetal and a trivalent metal is used as a metal deactivator, then (a)catalyst poison metals contained in a feedstock oil, such as nickel,vanadium and the like, can be efficiently deactivated, (b) a catalystcan be prepared regardless of the kind of the inorganic oxide matrix asa binder and the catalyst can be used as an FCC catalyst of either theone-body type or the additive type, and (c) a gasoline and an LCOfraction can be obtained in high yields while maintaining reducedselectivity to hydrogen and coke and without lowering the octane number,and these performances can be maintained on a high level over long. Thepresent invention has been thus completed.

[0020] The FCC catalyst of the present invention, which has beenaccomplished based on this finding, (1) comprises a compound which iseither a compound of a bivalent metal or a compound of bivalent andtrivalent metals showing an XRD pattern of a carbonate of the bivalentmetal.

[0021] In the catalyst, the compound may (2) have been dispersed in aninorganic oxide matrix or may (3) have been dispersed in an inorganicoxide matrix together with a crystalline aluminosilicate zeolite.

[0022] The FCC method of the present invention comprises using StandardCatalyst A obtained by evenly dispersing a crystalline aluminosilicatezeolite in an inorganic oxide matrix as a mixture with at least one ofCatalyst B described in (1) above, Catalyst C described in (2) above,and Catalyst D described in (3) above; Catalyst D as a mixture with atleast one of Catalyst B and Catalyst C; or Catalyst D alone.

BRIEF DESCRIPTION OF THE DRAWINGS

[0023]FIG. 1 shows an XRD pattern for MC-1 (Mn—Al—CO₃).

[0024]FIG. 2 shows an XRD pattern for MC-2 (Ca—Al—CO₃).

[0025]FIG. 3 shows an XRD pattern for MC-3 (Sr—Al—CO₃).

[0026]FIG. 4 shows an XRD pattern for MC-4 (Ba—Al—CO₃).

[0027]FIG. 5 shows an XRD pattern for MC-7 (Ca—CO₃).

[0028]FIG. 6 shows an XRD pattern for MC-8 (scallop shell Ca—CO₃).

[0029]FIG. 7 shows an XRD pattern for MC-9 (oystershell Ca—CO₃).

[0030]FIG. 8 shows an XRD pattern for a hydrotalcite.

BEST MODE FOR CARRYING OUT THE INVENTION

[0031] Catalyst B of the present invention described in (1) above has nocracking activity when used alone. It is an FCC catalyst of theso-called additive type, which is added to and used with an FCC catalystsuch as Standard Catalyst A described above, which has a crackingactivity.

[0032] Catalyst C described in (2) above is one in which the activeingredient of Catalyst B has been dispersed in an inorganic oxide matrixand which has enhanced mechanical strength. Catalyst C also has nocracking activity when used alone. Like Catalyst B, Catalyst C is an FCCcatalyst of the so-called additive type, which is added to and used withan FCC catalyst such as Standard Catalyst A.

[0033] Catalyst D described in (3) above is one in which the activeingredient of Catalyst B has been dispersed in an inorganic oxide matrixtogether with a crystalline aluminosilicate zeolite, which has acracking activity. Catalyst D has a cracking activity even when usedalone, and can be used as an FCC catalyst of the so-called one-bodytype.

[0034] The catalyst of the present invention comprising a compound of abivalent metal or a compound of bivalent and trivalent metals showing anXRD pattern of a carbonate of the bivalent metal (hereinafter referredto as a “compound of bivalent and trivalent metals”) and having on peakattributable to anion clay or the like is Catalyst B of the presentinvention.

[0035] Any bivalent and trivalent metals can be used as the bivalent andtrivalent metals. However, the bivalent metal is preferably at least oneselected from the group consisting of Mg²⁺, Mn²⁺, Ca²⁺, Sr²⁺, Ba²⁺, Sn²⁺and Zn²⁺, and is more preferably at least one selected from the groupconsisting of Mn²⁺, Ca²⁺, Sr²⁺, Ba²⁺ and Sn²⁺. The trivalent metal ispreferably at least one selected from the group consisting of Al³⁺,Fe³⁺, Cr³⁺, Co³⁺, La³⁺, Mn³⁺, Ti³⁺, Ga³⁺, Sb³⁺ and Bi³⁺, and is morepreferably at least one selected from the group consisting of Al³⁺ andMn³⁺. In particular, A³⁺ is the most preferable because it gives a largesurface area.

[0036] The compound of a bivalent metal and compound of bivalent andtrivalent metals described above can be a compound of any desiredcombination of at least one of the metals enumerated above.

[0037] Namely, the compound of a bivalent metal may be a compound havingone of those bivalent metals as the only bivalent metal, or may be acomposite compound having two or more of those in combination. In thiscase, the metals may be mixed in any proportion.

[0038] As the compound of bivalent and trivalent metals, a combinationof at least one member selected from Mn²⁺, Ca²⁺, Sr²⁺, Ba²⁺ and Sn²⁺with Al³⁺ is especially effective in deactivating catalyst poison metalsand removing SO_(x) because the catalyst efficiently adsorbs nickeloxides, vanadium oxides and sulfur oxides. In this case, at least twobivalent metals may be mixed in any proportion and at least twotrivalent metals may be mixed in any proportion. However, the proportionof the bivalent metals to the trivalent metals to be mixed therewith issuch that the bivalent metal/trivalent metal molar ratio is preferablyfrom 0.5 to 10, more preferably from 2 to 5.

[0039] When alumina is used as the inorganic oxide matrix in Catalysts Cand D, the bivalent-metal compound among the metal compounds ispreferably one having Ca²⁺, Sr²⁺ or Ba²⁺ because the catalyst has thehigh ability to deactivate catalyst poison metals.

[0040] When the compound of a bivalent metal or the compound of bivalentand trivalent metals is used as Catalyst B, a suitable form of thecompound is a particulate form having an average particle diameter equalto that of Standard Catalyst A or Catalyst C or D to be used incombination therewith, i.e., from 50 to 90 μm, a bulk density of from0.3 to 1.2 g/mL, and an oil absorption of 0.1 cc/g or more.

[0041] On the other hand, when the compound is mixed with an inorganicoxide matrix, a crystalline aluminosilicate zeolite, etc. and used as acomponent of Catalyst C or D, a suitable form thereof is a particulateform having an average particle diameter of from 0.0001 to 60 μm,preferably from 0.001 to 30 μm, and more preferably from 0.1 to 10 μm.When the particle diameter thereof exceeds 60 μm, Catalyst C or Dfinally obtained is undesirable as an FCC catalyst from the standpointsof bulk density, catalyst strength, etc. because such a particlediameter is equal to the average particle diameter of Catalyst C or D.When the particle diameter thereof is smaller than 0.0001 μm, handlingis difficult.

[0042] Examples of the compound of a bivalent metal and examples of thecompound of bivalent and trivalent metals include oxides, carbonates,sulfates, halide salts, phosphates and the like. Among these, carbonatesare preferable. The carbonates may be synthetic ones or natural ones,and commercial products can be used as they are.

[0043] When alumina is used as the inorganic oxide matrix in Catalysts Cand D, preferable carbonates are calcium carbonate, strontium carbonateand barium carbonate, in which the bivalent metals are Ca²⁺, Sr²⁺ andBa²⁺ from the standpoints of not only the ability to deactivate catalystpoison metals but also catalyst abrasion strength. In particular,calcium carbonate is most preferable because it has a lower truespecific gravity than strontium carbonate and barium carbonate, itprevents the finished catalyst from having an increased bulk density andmakes catalyst preparation easy, and that calcium carbonate isinnoxious, easy to handle, and easily available.

[0044] Synthetic carbonates can be obtained, for example, as follows.

[0045] The carbonate of a bivalent metal is obtained by adding anaqueous solution of a water-soluble salt of a bivalent metal to anaqueous solution of an alkali carbonate and regulating the pH thereofwith an aqueous alkali solution to obtain a slurry of a crystallinecarbonate.

[0046] When at least two bivalent metals are used in combination,aqueous solutions of water-soluble salts of the at least two bivalentmetals are mixed together beforehand and the mixture is treated in thesame manner as that described above to thereby obtain a slurry.

[0047] A carbonate of bivalent and trivalent metals is obtained bymixing beforehand an aqueous solution of a water-soluble salt of atleast one bivalent metal with an aqueous solution of a water-solublesalt of at least one trivalent metal and treating the mixture in thesame manner as that described above to thereby obtain a slurry.

[0048] The water-soluble salts described above may be either inorganicsalts or organic salts. Examples of the counter ions in the saltsinclude F⁻, Cl⁻, Br⁻, I⁻, NO₃ ⁻, CO₃ ²⁻, SO₄ ²⁻, PO₄ ³⁻, ClO₄ ⁻, BO₃ ²⁻,CH₃COO⁻, oxalic acid, salicylic acid and the like. Inexpensive Cl⁻, NO₃⁻, SO₄ ²⁻ and CO₃ ²⁻ are preferable.

[0049] There are cases where acid ions come into the gel during slurryaging, depending on the kind of such counter ions, and the acid ionsincorporated are difficult to remove completely. The residual acid ionsmay have adverse influence on the product catalyst. NO₃ ⁻ salts are themost preferable because the counter ion is apt to volatilize in aburning treatment and, hence, does not cause such a trouble.

[0050] With respect to the aqueous solution of an alkali carbonate towhich an aqueous solution of any of those water-soluble salts is to beadded, carbonates in which the alkali ions (counter cations) are NH₄, Naand K are preferable because they are generally inexpensive and easilyavailable. However, when the aged slurry is used without being subjectedto a washing treatment or the like, there are cases where ions come intothe gel during aging, depending on the kind of the alkali, and haveadverse influence on the product catalyst, as in the case of the saltsof bivalent metals and trivalent metals described above. NH₄ salts arepreferable because the counter ion is apt to volatilize in a burningtreatment and, hence, does not cause such a trouble.

[0051] The crystals in the thus-obtained slurry of a crystallinecarbonate are subjected to aging. The aging is preferably carried out ata pH of from 6 to 14 and a temperature of from 0 to 100° C. The agingmay be conducted for any time period.

[0052] In general, longer aging periods are advantageous in obtaininglarger crystal sizes (particle diameters), and shorter aging periods maybe used in obtaining smaller crystal sizes. Furthermore, the higher theaging temperature is, the higher the crystallinity is.

[0053] For obtaining crystal particles having the particle diametershown above, it is preferable that the aging is carried out for 0.5 to36 hours at a temperature of from 50 to 90° C. and a pH of from 8 to 11.Any crystalline carbonate thus obtained under such aging conditions issuitable for use as Catalyst B of the present invention or as acomponent of Catalyst C or D.

[0054] After the crystal aging, the crystalline-carbonate slurry can besubjected, without any treatment, to drying and particle diameterregulation so as to be used as Catalyst B, or can be used, without anytreatment, as a component of Catalyst C or D. However, it is preferableto use the slurry after it is washed with ammonia water or an aqueousammonium salt solution and with water to remove metallic and otherimpurities which may have adverse influence on the catalyst.

[0055] When the slurry is used as a component of Catalyst C or D, it maybe regulated so as to have a smaller particle diameter than the FCCcatalyst particles by subjecting the slurry to spray drying or to dryingand subsequent milling or the like. However, from the standpoint ofreducing the time period necessary for preparing Catalyst C or D, it ispreferable to regulate the particle diameter beforehand to the sizedescribed above and use the slurry.

[0056] The crystalline carbonate of a bivalent metal or of bivalent andtrivalent metals considerably changes in its basic nature through a heattreatment, and the basic nature has great influences on themetal-deactivating ability.

[0057] The crystalline carbonate of a bivalent metal or of bivalent andtrivalent metals used in the present invention can be dried and burnedat a temperature of from 20 to 900° C. However, from the standpoint ofenhancing the metal-deactivating ability, the treatment is conductedpreferably at a temperature of from 300 to 800° C., more preferably from500 to 700° C.

[0058] Examples of natural carbonates include ores, shells, and bones ofanimals.

[0059] Examples of ores include calcite, iceland spar, aragonite,limestone, marble, whiting, strontianite, witherite, rhodochrosite andthe like.

[0060] Any shells and animal bones can be used as the natural shells andanimal bones. Examples include shells of abalones, corbiculas,short-necked clams, clams, oysters, scallops, turbos and the like, andbones of cattle, pigs, horses, sheep, chickens, fishes and the like.They are easily available at low cost. In addition, when shells areused, they produce an effect that the abrasion strength of the catalystcan be enhanced.

[0061] The natural carbonates may be used alone, or at least two may besuitably selected therefrom and used as a mixture of these in anappropriate proportion.

[0062] In the case of shells or bones, organic matters, water and thelike are adhered thereto. It is therefore preferable to use shells orbones after they are washed, burned and then pulverized. The burning maybe conducted under any conditions so long as the organic matters, waterand the like can be removed. Suitable burning is conducted at atemperature of from 300 to 900° C. for about from 10 minutes to 5 hours,preferably at a temperature of from 500 to 800° C. for about from 30 to5 hours.

[0063] The shells or bones which have been burned under such conditionscan be relatively easily pulverized. They may be directly pulverizedwith a mill. Alternatively, they are primarily crushed with a water jetor the like and then secondarily pulverized with a wet mill, or areprimarily crushed with a hammer mill or the like and the secondarilypulverized with a dry mill. Thus, the burned shells or bones areregulated so as to have the average particle diameter described above.

[0064] Catalysts B and C, which are of the additive type, desirably havethe same material properties as Standard Catalyst A used in combinationtherewith or as Catalyst D, which is of the one-body type, used incombination therewith. When the catalysts differ from each other instrength, particle diameter or bulk density, there are cases where thecatalysts do not evenly mix with each other and are unable to exhibitsufficient catalytic performance.

[0065] The material properties of Catalysts A to D cannot beunconditionally determined because they vary depending on the kind ofthe FCC apparatus and operating conditions therefor. However, from thestandpoint of obtaining satisfactory flowability in FCC apparatus, thecatalysts generally preferably have an average particle diameter of from50 to 90 μm, a bulk density of from 0.3 to 1.2 g/mL, and an oilabsorption of 0.1 cc/g or more, as described above.

[0066] Catalyst C of the present invention comprises an inorganic oxidematrix and, dispersed therein, the compound of a bivalent metal or thecompound of bivalent and trivalent metals, and has no FCC activity.Namely, it is a catalyst of the additive type which is added to and usedwith an FCC catalyst having an FCC activity, such as Standard CatalystA, Catalyst D, etc.

[0067] In Catalyst C, the amount of the metal compound is preferablyfrom 1 to 90% by weight, and more preferably from 30 to 70% by weight,on a dry basis. When the amount thereof is less than 1% by weight, themetal-inactivating ability and SO_(x)-adsorbing ability are low. Evenwhen the amount thereof is increased to be more than 90% by weight, notonly substantially no enhancement in effect is obtained but also therelatively reduced amount of the inorganic oxide leads to a decrease inthe particle-bonding strength attributable to the inorganic oxide.

[0068] Examples of the inorganic oxide in Catalyst C include knowninorganic oxides used in ordinary cracking catalysts, such as silica,silica-alumina, alumina, silica-magnesia, alumina-magnesia,phosphorus-alumina, silica-zirconia, silica-magnesia-alumina and thelike. A clay such as kaolin, halloysite, montmorillonite, or the likemay be mixed with the inorganic oxides.

[0069] An especially preferable example of Catalyst C is a catalystcomprising a combination of alumina as the inorganic oxide and calciumcarbonate as the bivalent-metal compound, because it has the highability to deactivate catalyst poisons.

[0070] Catalyst C can be produced by adding the metal compound to theinorganic oxide, followed by evenly dispersion, spray-drying theresulting mixture slurry in the usual manner, washing the resultingparticles if necessary, and drying them again or drying/burning them.

[0071] In this operation, the metal compounds of some kinds may bedifficult, due to their basic nature, to evenly mix with the inorganicoxide or other catalyst ingredients optionally incorporated. In thiscase, it is preferable to reduce the basic nature of the metal compoundsby coating with phosphoric acid, coating with alumina or the like.

[0072] Catalyst D of the present invention comprises the compound of abivalent meal or compound of bivalent and trivalent metals, acrystalline aluminosilicate zeolite, and an inorganic oxide matrix inwhich the metal compound and zeolite are dispersed. The catalyst has themetal-deactivating effect attributable to the metal compound and furtherhas the FCC activity of the crystalline aluminosilicate zeolite.Catalyst D is hence a catalyst of the one-body type which can be usedalone as an FCC catalyst.

[0073] In Catalyst D, the amount of the metal compound is preferablyfrom 0.01 to 20% by weight, more preferably from 0.1 to 10% by weight,and most preferably from 0.5 to 5% by weight, on a dry basis.

[0074] When the amount thereof is less than 0.01% by weight, themetal-deactivating effect and SO_(x) trapping are insufficient. When theamount thereof is more than 20% by weight, the relative content of thecrystalline aluminosilicate zeolite or of the inorganic oxide decreasesand the FCC activity and selectivity to gasoline are reduced. Theresults not only make it difficult to catalytically crack a feedstockoil in a desired manner but also cause problems, for example, that thecatalyst strength decreases.

[0075] The amount of the crystalline aluminosilicate zeolite in CatalystD is preferably from 10 to 50% by weight, and more preferably from 20 to40% by weight, on a dry basis.

[0076] When the amount thereof is less than 10% by weight, the FCCactivity and selectivity to gasoline are reduced, making it difficult tocatalytically crack a feedstock oil in a desired manner. When the amountthereof is more than 50% by weight, the relative content of the metalcompound or of the inorganic oxide matrix decreases and the desiredmetal-deactivating effect is not obtained or the desired catalyststrength may not been obtained.

[0077] Examples of the inorganic oxide in Catalyst D include the sameinorganic oxides as those used in Catalyst C. Clays such as those foruse in Catalyst C may be incorporated into the inorganic oxide.

[0078] Examples of the crystalline aluminosilicate zeolite includezeolites X, zeolites Y, zeolites β, mordenite, zeolites ZSM, naturalzeolites and the like. Similar to the ordinary FCC catalysts, thezeolites can be used in a form ion-exchanged with a cation selected fromhydrogen, ammonium and polyvalent metals.

[0079] Zeolites Y are especially preferable, and zeolite USY, which hasexcellent hydrothermal stability, is most preferable.

[0080] The most preferable zeolite is a heat-shock crystallinealuminosilicate zeolite (hereinafter referred to as “HS zeolite”) whichis obtained by burning a stabilized zeolite Y having an SiO₂/Al₂O₃ molarratio of from 5 to 15, a unit lattice size of from 24.50 Å to less than24.70 Å, and an alkali metal content (in terms of oxide) of from 0.02%by weight to less than 1% by weight at from 600 to 1,200° C. for from 5to 300 minutes in an air or nitrogen atmosphere so as to result in adecrease in the crystallinity of the stabilized zeolite Y of 20% orless. In the zeolite, the SiO₂/Al₂O₃ molar ratio in the bulk is from 5to 15 and the molar ratio of the aluminum present in the zeoliteframework to all aluminum is from 0.3 to 0.6. The zeolite has a unitlattice size less than 24.45 Å and an alkali metal content (in terms ofoxide) of from 0.02% by weight to less than 1% by weight and has a poredistribution having characteristic peaks at around 50 Å and 180 Å inwhich the volume of the pores of at least 100 Å is from 10 to 40% of thetotal pore volume. The zeolite has an X-ray diffraction pattern which isa main pattern for zeolites Y (See Japanese Patent No. 2,544,317.)

[0081] Catalyst D can be produced by adding the zeolite and the metalcompound to an inorganic oxide, followed by even dispersion to therebyprepare a mixture slurry, and treating the slurry in the same manner asin the production of Catalyst C described above.

[0082] In this production, the metal compound may be difficult, due toits basic nature, to evenly mix with the inorganic oxide or crystallinealuminosilicate zeolite or with other catalyst ingredients optionallyincorporated. In this case, the basic nature of the metal compound canbe reduced by coating with phosphoric acid, coating with alumina and thelike, as in the production of Catalyst C.

[0083] Standard Catalyst A, which may be used in combination with atleast one of Catalysts B to D described above, comprises a matrixcomprising an inorganic oxide and a crystalline aluminosilicate zeoliteevenly dispersed in the matrix. Any of various cracking catalystsordinary used can be used.

[0084] Examples of the inorganic oxide and crystalline aluminosilicatezeolite include those which are the same as in Catalysts C and D of thepresent invention described above.

[0085] In FCC catalysts ordinary used, the amount of the crystallinealuminosilicate zeolite dispersed in a matrix comprising the inorganicoxide or comprising it and a clay is about from 10 to 50% by weight, andpreferably about from 20 to 40% by weight. In the present invention,however, the proportion of mixed Catalyst B, C or D should be taken intoaccount because Catalyst B, C or D is used in combination with StandardCatalyst A.

[0086] Specifically, it is suitable to regulate the amount of thecrystalline aluminosilicate zeolite to at least 10% by weight,preferably from 10 to 50% by weight, and more preferably from 20 to 40%by weight, based on the total amount of Catalysts A, B, C and D.

[0087] When the amount of the zeolite is less than 10% by weight, thedesired FCC activity cannot be obtained. Even when the amount thereof isincreased to be 50% by weight or more, the effect of mixing the zeoliteis not enhanced any more. Therefore, such large zeolite amounts areuneconomical.

[0088] For obtaining the desired zeolite proportion, it is advantageousto regulate beforehand the zeolite amount in the FCC catalyst.

[0089] Standard Catalyst A desired above can be produced by adding thecrystalline aluminosilicate zeolite to the inorganic oxide, followed byeven dispersion, spray-drying the resulting mixture slurry in the usualmanner, washing the resulting particles if necessary, and drying theseagain or burning the particles after drying.

[0090] The FCC method of the present invention is conducted using atleast one of the additive type catalysts B and C described above and theone-body type Catalyst D described above in combination with StandardCatalyst A, or using the one-body type Catalyst D in combination with atleast one of the additive type Catalysts B and C, or using the one-bodytype Catalyst D alone.

[0091] When at least one of Catalysts B to D is used in combination withStandard Catalyst A, the proportions of the catalysts used aredetermined while taking account of the following.

[0092] When Standard Catalyst A is used in combination with Catalyst D,any proportions thereof may be selected according to the desiredmetal-deactivating ability and desired SO_(x)-trapping ability.

[0093] When either or both of Catalysts A and D are used in combinationwith either or both of Catalysts B and C, it is suitable that (either orboth of Catalysts A and D)/(either or both of Catalysts B and C) is from99.9/0.1 to 50/50, preferably from 99.5/0.5 to 80/20, and morepreferably from 99/1 to 90/10, in terms of weight ratio. When either orboth of the additive type Catalysts B and C account for more than a halfof the total catalyst amount, the FCC activity and selectivity togasoline are reduced, making it difficult to catalytically crack afeedstock oil in a desired manner.

[0094] In the FCC method of the present invention, Catalysts A to D maybe used as independent particulate catalysts in the proportion describedabove or used as particles of a catalyst mixture prepared beforehand inthe proportion described above. FCC can be accomplished by bringing aheavy hydrocarbon oil as a feedstock oil into contact with the catalystparticles under FCC conditions.

[0095] Examples of the heavy hydrocarbon oil is, for example, vacuumdistillation gas oil, topping residue, vacuum distillation residue, ablend of these and the like.

[0096] The FCC catalyst of the present invention is effective even whena heavy hydrocarbon oil reduced in the contents of nickel or vanadiumcompounds and of sulfur compounds is used as a feedstock oil. However,the catalyst is extremely useful when it is used for the catalyticcracking of a low-quality heavy hydrocarbon oil containing catalystpoison metals and sulfur compounds in large amounts (e.g., having asulfur content of 0.2% by weight or more and a metal content of 50 ppm(in terms of metal amount) or more). Consequently, the FCC method of thepresent invention can provide a remarkable effect when such alow-quality heavy hydrocarbon oil is used as a feedstock oil.

[0097] In practicing the FCC method of the present invention, the amountof the metal contaminants and sulfur compounds contained in thefeedstock oil is taken into account. When the amount thereof is large, amixture of Standard Catalyst A or one-body type Catalyst D with theadditive type Catalyst B or C may be used so that the additive typeCatalyst B or C is contained in an increased proportion. Thus, thedecrease in FCC activity which may occur due to the relatively reducedamount of Standard Catalyst A or one-body Catalyst D can be compensatedfor by the increase in the amount of the crystalline aluminosilicatezeolite dispersed in Standard Catalyst A or one-body type Catalyst D.

[0098] The FCC conditions used in the present invention can be FCCconditions ordinary used. Typical examples of the FCC conditions are asfollows:

[0099] Reaction temperature: 460-540° C.

[0100] WHSV: 4-20 hr⁻¹

[0101] Catalyst/oil ratio: 4-12

[0102] In FCC processes, FCC catalysts which have been deactivated bycoke deposition are generally regenerated by carbon burning and reusedin FCC reactions. In the FCC catalyst and FCC method of the presentinvention, too, Standard Catalyst A, one-body type Catalyst D, andadditive type Catalysts B and C which have been spent can be regeneratedwith an existing regenerator under usual regeneration conditions andreused.

[0103] The regeneration is conducted at a temperature of from 600 to750° C. Catalysts B to D of the present invention show an excellenteffect in trapping the SO_(x) which generates during this regeneration.

[0104] Catalysts B to D of the present invention deactivate catalystpoison metals contained in feedstock oils, e.g., nickel and vanadium,are reduced in the amount of hydrogen and coke yielded and excellent incracking activity and bottom oil-treating ability, and can yield agasoline and an LCO fraction in high yields. Furthermore, the catalystscan retain the performances on a high level over long and hence have animproved catalyst life. In addition, since the catalysts adsorb SO_(x)in a large amount, they are effective in reducing the amount of SO_(x)contained in the discharge gas from the FCC apparatus.

EXAMPLES

[0105] Catalyst Preparation:

[0106] 1. Preparation of Crystalline Metal Compounds Comprising BivalentMetal or Comprising Bivalent and Trivalent Metals

Example 1

[0107] In a 3-liter (hereinafter, liter is referred to as “L” andmilliliter is referred to as “mL”) glass beaker containing 1,000 mL ofdistillation-purified water, 271.9 g of manganese sulfate pentahydratewas dissolved, followed by stirring with a magnetic stirrer for 15minutes to prepare Solution A. Solution A had a pH of 4.54.

[0108] In a 3-L glass beaker containing 1,000 mL ofdistillation-purified water, 125 g of aluminum sulfate octadecahydratewas dissolved, followed by stirring with a magnetic stirrer for 15minutes to prepare Solution B. Solution B had a pH of 1.63.

[0109] Solution A was mixed with Solution B in a 5-L glass beaker,heated to 80° C. and stirred with a magnetic stirrer to prepare SolutionC.

[0110] In a 5-L glass beaker containing 1,000 mL ofdistillation-purified water, 113.8 g of sodium carbonate was dissolved,followed by heating to 80° C. and stirring with an ultradisperser for 15minutes to prepare Solution D. Solution D had a pH of 11.47.

[0111] While stirring Solution D with an ultradisperser, Solution C wasgradually added thereto with a feed pump. During the operation, ammoniawater was also added to keep the pH of the solution mixture at 9.

[0112] The solution mixture was subjected to aging with stirring at 80°C. for 3 hours to yield a metal compound.

[0113] After termination of the aging, the solution was filtered througha Buchner funnel. To the slurry (metal compound) separated, 2 L ofdistillation-purified water heated to 80° C. was added. The resultingmixture was stirred and filtered. The operation was repeated to conductwashing twice.

[0114] The slurry separated by filtration was dried at 100° C. for about24 hours to obtain a metal compound.

[0115] The metal compound which had been dried was pulverized with amill to a particle diameter of 15 μm or less.

[0116] The metal compound is referred to as MC-1 (Mn—Al—CO₃).

[0117] APS (average particle diameter) and SA (specific surface area) ofMC-1 were examined and the metal composition was ascertained with an ICPapparatus. The results are shown in Table 1. Before being examined byICP, samples were subjected to a burning treatment at 1,100° C. for 2hours as a pretreatment.

[0118] Furthermore, an XRD apparatus was used to analyze the crystalstructure. The results are shown in FIG. 1.

[0119] In FIG. 1, the results of the analysis with the XRD apparatus areshown in the upper section, peak data are shown in the middle section,and the Mn—Al—CO₃ data from JCPDS-PDF (Joint Committee on PowerDiffraction Standards-Power Diffraction; data bank dealing with acollection of X-ray powder diffraction data) are shown in the lowersection.

[0120]FIG. 1 clearly shows that MC-1 has the crystal structure of abivalent-metal carbonate.

Example 2

[0121] Crystalline metal compounds were prepared in the same manner asin Example 1, except that the bivalent metal was replaced with Ca²⁺,Sr²⁺, Ba²⁺ or Sn²⁺ by using the chloride or nitrate of the metal inSolution A in Example 1 in an amount equimolar to the manganese sulfate.

[0122] The crystalline metal compounds prepared using Ca²⁺, Sr²⁺, Ba²⁺and Sn²⁺ as bivalent metals are referred to as MC-2 (Ca—Al—CO₃), MC-3(Sr—Al—CO₃), MC-4 (Ba—Al—CO₃) and MC-5 (Sn—Al—CO₃), respectively.

[0123] APS and SA of MC-2, MC-3, MC-4 and MC-5 were examined, and themetal compositions were ascertained with an ICP apparatus. The resultsare shown in Table 1.

[0124] Furthermore, an XRD apparatus was used to analyze the crystalstructures of MC-2 to MC-4. The results are shown in FIGS. 2 to 4. InFIGS. 2 to 4, the data in the upper, middle, and lower sections have thesame meanings as in FIG. 1. FIGS. 2 to 4 clearly show that each of MC-2to MC-4 has the crystal structure of a bivalent-metal carbonate.

Example 3

[0125] A crystalline metal compound was prepared in the same manner asin Example 1, except that the trivalent metal was replaced with an othermetal by using the sulfate or nitrate of the trivalent metal in SolutionB in Example 1 in an amount equimolar to the aluminum sulfate.

[0126] The crystalline metal compound prepared using Mn³⁺ as a trivalentmetal is referred to as MC-6 (Mn—Mn—CO₃).

[0127] APS and SA of MC-6 was examined, and the metal composition wasascertained with an ICP apparatus. The results are shown in Table 1.

Example 4

[0128] The first-grade reagent of calcium carbonate manufactured byKanto Chemical Co., Inc. is referred to as MC-7 (CaCO₃); and powdersprepared from scallop shells and oystershells by burning at 700° C. for2 hours and subsequent pulverization are referred to as MC-8 (CaCO₃) andMC-9 (CaCO₃), respectively.

[0129] APS and SA of MC-7, MC-8 and MC-9 were examined, and the metalcompositions were ascertained with an ICP apparatus. The results areshown in Table 1.

[0130] Furthermore, an XRD apparatus was used to analyze the crystalstructures of MC-7 to MC-9. The results are shown in FIGS. 5 to 7. InFIGS. 5 to 7, the data in the upper, middle, and lower sections have thesame meanings as in FIG. 1. FIGS. 5 to 7 clearly show that each of MC-7to MC-9 has the crystal structure of a bivalent-metal carbonate. TABLE 1dry basis (wt %) Hydrotalcite MC-1 MC-2 MC-3 MC-4 MC-5 MC-6 MC-7 MC-8MC-9 Al₂O₃ 34.7 18.58 34.63 24.53 15.61 10.03 — — 0.4 0.3 MgO 60 — — — —— — — 0.11 0.1 Mn₂O₃ — 77.32 — — — — 98.45 — 0.04 0.06 CaO — — 63.81 — —— — 99.5 96.11 92.45 Sr₂O₃ — — — 73.91 — — — — 0.1 — BaO — — — — 84.03 —— — — — SnO₂ — — — — — 89.89 — — — — Na₂O — — 1.56 1.56 0.36 0.08 — —0.3 0.35 K₂O — — — — — — — — 0.06 0.07 APS (μm) 0.5 2 3.6 1.3 1.1 1.61.5 1.7 2.7 3.5 SA (m²/g) 150 104 27 24 32 53 12 2 5.9 6.9

[0131] 2. Preparation of Catalysts

Example 5

[0132] To 400 g of a silica hydrosol containing 10% by weight SiO₂, 64 gof HS zeolite and 86 g of kaolin clay on a dry basis were added tothereby obtain a mixture slurry.

[0133] The mixture slurry was spray-dried so as to result in particleshaving an average particle diameter of 68±5 μm. The particles werewashed and then dried again to obtain Standard Catalyst A.

[0134] Standard Catalyst A is referred to as Base 1. It was used as areference mainly for comparison with one-body type Catalyst D.

[0135] On the other hand, Standard Catalyst A was produced on acommercial scale in an amount of about 100 tons through one operation.The catalyst is referred to as Base 2. It was used as a reference mainlyfor the evaluation of additive-type Catalysts B and C.

[0136] APS, SA, ABD (apparent bulk density) and PV (pore volume) ofStandard Catalysts A (Bases 1 and 2) were examined. The results areshown in Tables 2 and 3.

Example 6

[0137] To 400 g of a silica hydrosol containing 10% by weight SiO₂, 64 gof HS zeolite and 86 g of kaolin clay on a dry basis were added, and 10g of a metal compound having a particle diameter of 15 μm or lessprepared in Examples 1 and 2 was prepared to thereby obtain a mixtureslurry.

[0138] The mixture slurry was spray-dried so as to result in particleshaving an average particle diameter of 68±5 μm. The particles werewashed and then dried again to obtain one-body type Catalyst D havingthe metal compound fixed thereto.

[0139] One-body type catalysts using MC-1, MC-2, MC-5, MC-7 andhydrotalcite KW-2200 manufactured by Kyowa Chemical Co., Ltd. as themetal compound are referred to as Catalysts D1, D2, D3, D4 and X,respectively.

[0140] APS, SA, ABD and PVC of Catalysts D1, D2, D3 and D4 wereexamined. The results are all shown in Table 2.

[0141] Furthermore, the metal compositions were ascertained with an ICPapparatus. As a result, the catalysts were ascertained to contain themetal compounds in an amount of about 5% by weight on a dry basis.

[0142] The hydrotalcite KW-2200, manufactured by Kyowa Chemical Co.,Ltd., was dried at 100° C. Thereafter, the hydrotalcite was examined byXRD and the hydrotalcite structure was ascertained. The results areshown in FIG. 8. TABLE 2 Catalyst name Base 1 X D1 Catalyst composition:Metal deactivator — hydrotalcite MC-1 Binder silica silica silicaZeolite HS zeolite HS zeolite HS zeolite Matrix kaolin kaolin kaolinCatalyst property: APS (μm) 68 71 70 SA (m²/g) 223.9 185.5 212.2 ABD(g/mL) 0.78 0.71 0.71 PV (mL/g) 0.16 0.14 0.16 Catalyst name D2 D3 D4Catalyst composition: Metal deactivator MC-2 MC-5 MC-7 Binder silicasilica silica Zeolite HS zeolite HS zeolite HS zeolite Matrix kaolinkaolin kaolin Catalyst property: APS (μm) 70 70 68 SA (m²/g) 178.4 193133 ABD (g/mL) 0.73 0.75 0.69 PV (mL/g) 0.16 0.15 0.16

Example 7

[0143] To 600 g of a silica hydrosol containing 10% by weight SiO₂, 40 gon a dry basis of a metal compound having a particle diameter of 15 μmor less prepared in Examples 1 to 4 was added to thereby obtain amixture slurry.

[0144] The mixture slurry was spray-dried so as to result in particleshaving an average particle diameter of 68±5 μm. The particles werewashed and then dried to obtain additive type Catalyst C having themetal compound fixed thereto.

[0145] Additive type Catalysts C using MC-1 and hydrotalcite KW-2200manufactured by Kyowa Chemical Co., Ltd. as the metal compound arereferred to as Catalysts C1 and Y, respectively.

[0146] APS, SA, ABD and PV of Catalysts C1 and Y were examined. Theresults are shown in Table 3.

[0147] Furthermore, the metal compositions were ascertained with an ICPapparatus. As a result, the catalysts were ascertained to contain themetal compounds in an amount of about 40% by weight on a dry basis.TABLE 3 Catalyst name Base 2 Y C1 Additive composition: Metaldeactivator — hydrotalcite MC-1 Binder — silica silica Zeolite — — —Matrix — — — Catalyst property: APS (μm) 65 67 67 SA (m²/g) 189.2 83.297.6 ABD (g/mL) 0.72 0.64 0.67 PV (mL/g) 0.15 0.22 0.245 Additiveproportion: Base 2 (wt %) 100 90 90 Additive type (wt %) 0 10 10

Example 8

[0148] To 3 kg of an alumina hydrogel slurry containing 10% by weightAl₂O₃, 200 g on a dry basis of a metal compound having a particlediameter of 15 μm or less prepared in Examples 1 to 4 was added. Theslurry was spray-dried so as to result in particles having an averageparticle diameter of 68±5 μm. Thus, an additive type Catalyst C havingthe metal compound fixed thereto was obtained.

[0149] Additive type catalysts were obtained using MC-1, MC-2, MC-3,MC-4, MC-5, MC-6, MC-7, MC-8 and MC-9 as the metal compound are referredto as Catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10, respectively.

[0150] APS, SA, ABD and PV of Catalysts C2, C3, C4, C5, C6, C7, C8, C9and C10 were examined. Catalysts C3, C8, C9 and C10 were furtherexamined for catalyst abrasion strength [initial fine (referred to as“IF”) and average attrition loss (referred to as “AL”)]. The results areshown in Table 4.

[0151] Furthermore, the metal compositions were ascertained with an ICPapparatus. As a result, the catalysts were ascertained to contain themetal compounds in an amount of about 40% by weight on a dry basis.

[0152] Moreover, 3 kg of an alumina hydrogel slurry containing 10% byweight Al₂O₃ was spray-dried so as to result in particles having anaverage particle diameter of 68±5 μm. The catalyst thus obtained isreferred to as Catalyst Z.

[0153] APS, SA, ABD and PV of Catalyst Z was examined. The results areshown in Table 4. TABLE 4 Catalyst name Base 2 Z C2 C3 Additivecomposition: Metal deactivator — — MC-1 MC-2 Kind of binder — aluminaalumina alumina Zeolite — — — — Matrix — — — — Catalyst property: APS(μm) 65 69 68 64 SA (m²/g) 189.2 259 205 184 ABD (g/mL) 0.72 0.54 0.50.67 PV (mL/g) 0.15 0.652 0.715 0.322 IF — — — 17.87 AL — — — 20.61Additive proportion: Base 2 (wt %) 100 90 90 90 Additive type (wt %) 010 10 10 Catalyst name C4 C5 C6 C7 Additive composition: Metaldeactivator MC-3 MC-4 MC-5 MC-6 Kind of binder alumina alumina aluminaalumina Zeolite — — — — Matrix — — — — Catalyst property: APS (μm) 65 6865 67 SA (m²/g) 201 174 186 145 ABD (g/mL) 0.67 0.78 0.84 0.7 PV (mL/g)0.271 0.294 0.28 0.23 IF — — — — AL — — — — Additive proportion: Base 2(wt %) 90 90 90 90 Additive type (wt %) 10 10 10 10 Catalyst name C8 C9C10 Additive composition: Metal deactivator MC-7 MC-8 MC-9 Kind ofbinder alumina alumina alumina Zeolite — — — Matrix — — — Catalystproperty: APS (μm) 73 69 68 SA (m²/g) 133 176.7 192.5 ABD (g/mL) 0.780.81 0.83 PV (mL/g) 0.201 0.207 0.195 IF 12.6 6.63 7.01 AL 17.65 3.142.87 Additive proportion: Base 2 (wt %) 90 90 90 Additive type (wt %) 1010 10

[0154] 3. Analytical Instruments, Analytical Conditions, etc.

[0155] The instruments and expressions for calculation or the like usedin the analyses described above are as follows.

[0156] ICP (Compositional Analysis):

[0157] “IRIS Advantage” manufactured by Thermo Jarrell Ash APS (averageparticle diameter):

[0158] “Electromagnetic Vibrating Microsifter Type M-2” manufactured byTsutsui Rikagaku Kiki K.K.

[0159] SA (Specific Surface Area):

[0160] “BELSORP 28” (high-precision, fully automatic gas adsorber)manufactured by Bel Japan Inc.

[0161] ABD (Apparent Bulk Density):

[0162] “Bulk Density Meter” manufactured by Tokyo

[0163] Kuramochi Kagaku Kikai Seisakusho (JIS Z 2504)

[0164] PV (Pore Volume):

[0165] “MICROMERITICS AUTOPORE II 9220” manufactured by Shimadzu Corp.

[0166] IF (Initial Fine)*:

[0167] [(Fine particles in 0-12 hours (dry g))/(sample amount)]×100

[0168] AL (Average Attrition Loss)*:

[0169] [(Fine particles in 12-42 hours (dry g))/(sample amount)]×100

[0170] * The initial fine and average attrition loss were determinedthrough a catalyst abrasion strength test conducted as follows andthrough calculation.

[0171] Fifty grams of a catalyst (sample) was treated by heating at 500°C. for 5 hours, 5 g of water was added thereto, and the catalyst wasflowed through a catalyst pipe at a flow rate of 0.102 m/sec. The amountof fine particles (dry g) present in the catalyst pipe was measured atthe time when 12 hours had passed since initiation of the flowing (0-12hours) and at the time when 42 hours had passed thereafter (12-42hours). The initial fine and average attrition loss were calculatedusing the expressions given above. XRD* apparatus:

[0172] “RINT 2500V” manufactured by Rigaku Corp.

[0173] * XRD analysis was conducted under the following conditions usinga sample prepared by drying each catalyst at 100° C. for 24 hours:

[0174] Tube voltage: 50 kV

[0175] Tube current: 300 mA

[0176] Scanning mode: continuous

[0177] Scanning speed: 2°/min

[0178] Scanning step: 0.02°

[0179] Range of scanning (2θ): 5-90°

[0180] Divergence/scattering slit: 1°

[0181] Light-receiving slit: 0.3 mm

[0182] 4. MAT Activity Test

[0183] Evaluation Conditions:

[0184] The catalysts obtained in Examples 5 to 8 were subjected to thefollowing simulated equilibration treatment. Thereafter, the catalystswere evaluated for FCC activity and metal-deactivating ability using afixed-bed micro activity test apparatus in accordance with ASTM (3907)and using hydrocarbon oils having the properties shown in Table 5 underthe following test conditions.

[0185] Conditions for Simulated Equilibration Treatment:

[0186] Each fresh catalyst was heated from room temperature to 500° C.over 30 minutes and held at 500° C. for 5 hours to burn it.

[0187] Thereafter, a cyclohexane solution containing nickel naphthenateand vanadium naphthenate in given amounts (1,000 and 2,000 ppm byweight) was infiltrated into each catalyst.

[0188] The catalyst was dried at 100° C., subsequently heated from roomtemperature to 500° C. over 30 minutes, and then held at 500° C. for 5hours to burn it again.

[0189] Subsequently, each catalyst in a fluidized state was heated fromroom temperature to 800° C. over 90 minutes in an air atmosphere. Afterthe temperature had reached 800° C., the atmosphere was replaced with a100% steam atmosphere to treat the catalyst therewith for 6 hours.

[0190] After this steam treatment, each catalyst was evaluated for FCCactivity.

[0191] In evaluating the metal-deactivating ability of each catalyst,the provided amounts of nickel and vanadium on the catalyst wereregulated to 0 and 0 ppm by weight, 1,000 and 2,000 ppm by weight, 2,000and 4,000 ppm by weight, or 3,000 and 6,000 ppm by weight. TABLE 5Hydrocarbon oils tested: vacuum distillation gas oils Sample 1 2 Density15° C. g/cm³ 0.8959 0.8819 Vacuum distillation IBP 319 294  5% ° C. 362352 10% ° C. 383 367 20% ° C. 406 390 30% ° C. 421 402 40% ° C. 433 41550% ° C. 446 424 60% ° C. 460 436 70% ° C. 481 451 80% ° C. 509 471 90%° C. 566 506 95% ° C. 531 97% ° C. 544 End point ° C. 605 548 Totaldistillate amount % 93.5 98.5 Residue amount % 6.5 1.5 Loss % 0 0 Pourpoint ° C. 33 35 Dynamic viscosity 50° C. mm²/S 34.54 18.67 Nitrogencontent 0.05 0.02 (chemiluminescence method) wt % Sulfur content (X-raymethod) wt % 0.15 0.01 Refractive index 70 nD 1.48 1.47 Density 70° C.g/cm³ 0.86 0.84 Molecular weight 475 402 (calculated from viscosity)Asphaltene (UOP) wt % 0.38 n-d-m (70° C.) % CA 15.2 12.8 % CN 14.6 18.8% CP 70.2 68.4 Aniline point (U-tube method) ° C. 95.4 94.5 Dynamicviscosity 75° C. mm²/S 14.56 8.77 Dynamic viscosity 100° C. mm²/S 7.674.99 Basic nitrogen wt % 0.0014 Bromine number gBr₂/100 g 1.90 Hydrogencontent wt % 13.03 Carbon residue content wt % 1.25 0.06

[0192] Test Conditions: Fixed Bed

[0193] Reaction temperature: 500° C.

[0194] Catalyst/hydrocarbon oil weight ratio: 2.5, 3.0, 3.5

[0195] Test period: 75 seconds

[0196] 5. Evaluation of Catalyst Performance

Example 9

[0197] One-body type Catalysts D1, D2, D3 and D4 containing MC-1, MC-2,MC-5 and MC-7, respectively, were subjected to the simulatedequilibration treatment and then to the MAT activity test using Sample2. The results are shown in Table 21.

Example 10

[0198] Catalyst X was subjected to the simulated equilibration treatmentand then to the MAT activity test using Sample 2. The results are alsoshown in Table 21. TABLE 21 Catalyst name Base 1 X D1 Metal deactivatorname — Hydrotalcite MC-1 Conversion (wt %): Catalyst/oil 3 3 3 Metalprovided amount: Ni/V (ppm)   0/0 73.13 58.56 73.49 1000/2000 67.7056.34 68.83 2000/4000 55.50 49.53 60.25 3000/6000 30.64 36.16 54.43Selectivity (wt %): Metal provided amount: Ni/V = 2000/4000 (ppm)Conversion (wt %) 60.00 60.00 60.00 Yield of each ingredient (wt %) H₂0.20 0.36 0.16 C1-2 1.43 2.02 1.31 LPG 11.93 12.49 12.05 GASO 43.3940.39 43.79 LCO 24.38 20.51 25.71 HCO+ 15.62 19.49 14.29 COKE 3.05 4.742.69 RON 88.49 88.41 88.40 Catalyst name D2 D3 D4 Metal deactivator nameMC-2 MC-5 MC-7 Conversion (wt %): Catalyst/oil 3 3 3 Metal providedamount: Ni/V (ppm)   0/0 72.62 72.71 72.19 1000/2000 67.97 68.70 67.722000/4000 57.48 58.90 55.95 3000/6000 46.43 51.28 41.68 Selectivity (wt%): Metal provided amount: Ni/V = 2000/4000 (ppm) Conversion (wt %)60.00 60.00 60.00 Yield of each ingredient (wt %) H₂ 0.19 0.17 0.21 C1-21.41 1.31 1.56 LPG 11.92 12.36 12.99 GASO 43.59 43.18 42.03 LCO 24.6025.23 22.98 HCO+ 15.40 14.77 17.02 COKE 2.89 2.98 3.21 RON 88.53 88.3888.46

Example 11

[0199] Additive type Catalyst C1 containing MC-1 was physically mixed inan amount of 10% by weight with Catalyst Base 2. The resulting catalystwas subjected to the simulated equilibration treatment and then to theMAT activity test using Sample 2. The results are shown in Table 31.

Example 12

[0200] Additive type Catalyst Y containing hydrotalcite KW-2200 wasphysically mixed in an amount of 10% by weight with Catalyst Base 2. Theresulting catalyst was subjected to the simulated equilibrationtreatment and then to the MAT activity test using Sample 2. The resultsare also shown in Table 31. TABLE 31 Catalyst name Base 2 Y C1 Metaldeactivator name — Hydrotalcite MC-1 Conversion (wt %): Catalyst/oil 3 33 Metal provided amount: Ni/V (ppm)   0/0 70.93 66.71 70.19 1000/200063.21 56.29 64.89 2000/4000 51.65 48.18 58.70 3000/6000 27.36 35.5251.98 Selectivity (wt %): Metal provided amount: Ni/V = 2000/4000 (ppm)Conversion (wt %) 60.00 60.00 60.00 Yield of each ingredient (wt %) H₂0.20 0.29 0.15 C1-2 1.28 1.30 1.23 LPG 12.06 12.08 12.56 GASO 43.4743.36 43.59 LCO 24.76 24.67 26.57 HCO+ 15.24 15.33 13.43 COKE 2.99 2.972.47 RON 88.43 88.35 88.65

Example 13

[0201] Additive type Catalysts C2, C3, C4, C5, C6, C7, C8, C9 and C10containing MC-1, MC-2, MC-3, MC-4, MC-5, MC-6, MC-7, MC-8 and MC-9,respectively, were physically mixed in an amount of 10% by weight withCatalyst Base 2. The resulting catalysts were subjected to the simulatedequilibration treatment and then to the MAT activity test usingSample 1. The results are shown in Table 41.

Example 14

[0202] Additive type Catalyst Z was physically mixed in an amount of 10%by weight with Catalyst Base 2. The resulting catalyst was subjected tothe simulated equilibration treatment and then to the MAT activity testusing Sample 1. The results are also shown in Table 41. TABLE 41Catalyst name Base 2 Z C2 C3 Metal deactivator name — — MC-1 MC-2Conversion (wt %): Catalyst/oil 3 3 3 3 Metal provided amount: Ni/V(ppm)   0/0 67.71 67.29 68.07 67.21 1000/2000 59.96 62.48 66.62 65.682000/4000 48.77 53.43 62.38 64.08 3000/6000 23.51 35.45 61.03 61.99Selectivity (wt %): Metal provided amount: Ni/V = 1000/2000 (ppm)Conversion (wt %) 60.00 60.00 60.00 60.00 Yield of each ingredient (wt%) H₂ 0.35 0.43 0.20 0.15 C1-2 0.84 0.96 0.83 0.76 LPG 12.50 11.61 12.2712.26 GASO 43.81 43.50 44.78 44.97 LCO 27.97 29.34 29.78 29.63 HCO+12.03 10.66 10.22 10.37 COKE 2.50 3.50 1.92 1.86 RON 89.37 89.41 89.0689.58 Selectivity (wt %): Metal provided amount: Ni/V = 3000/6000 (ppm)Conversion (wt %) 60.00 60.00 60.00 60.00 Yield of each ingredient (wt%) H₂ — — 0.33 0.36 C1-2 — — 0.91 0.91 LPG — — 12.93 12.62 GASO — —43.38 43.77 LCO — — 27.79 26.68 HCO+ — — 12.21 13.32 COKE — — 2.45 2.34RON — — 89.52 89.81 Catalyst name C4 C5 C6 C7 Metal deactivator nameMC-3 MC-4 MC-5 MC-6 Conversion (wt %): Catalyst/oil 3 3 3 3 Metalprovided amount: Ni/V (ppm)   0/0 67.33 67.80 67.36 67.45 1000/200065.97 66.14 64.81 63.49 2000/4000 63.89 63.83 57.65 58.40 3000/600062.43 61.81 43.18 50.22 Selectivity (wt %): Metal provided amount: Ni/V= 1000/2000 (ppm) Conversion (wt %) 60.00 60.00 60.00 60.00 Yield ofeach ingredient (wt %) H₂ 0.16 0.15 0.22 0.26 C1-2 0.79 0.85 0.81 0.71LPG 12.28 12.08 12.71 11.96 GASO 44.87 44.86 44.02 44.93 LCO 29.91 29.6928.91 29.51 HCO+ 10.09 10.31 11.09 10.49 COKE 1.90 2.06 2.24 2.14 RON89.33 89.30 89.21 89.17 Selectivity (wt %): Metal provided amount: Ni/V= 3000/6000 (ppm) Conversion (wt %) 60.00 60.00 60.00 60.00 Yield ofeach ingredient (wt %) H₂ 0.32 0.30 — — C1-2 0.87 0.92 — — LPG 12.8212.73 — — GASO 43.64 43.67 — — LCO 26.82 26.96 — — HCO+ 13.18 13.04 — —COKE 2.35 2.38 — — RON 89.67 89.62 — — Catalyst name C8 C9 C10 Metaldeactivator name MC-7 MC-8 MC-9 Conversion (wt %): Catalyst/oil 3 3 3Metal provided amount: Ni/V (ppm)   0/0 67.55 68.32 67.75 1000/200065.74 66.09 65.92 2000/4000 63.98 63.92 64.21 3000/6000 61.54 62.0761.84 Selectivity (wt %): Metal provided amount: Ni/V = 1000/2000 (ppm)Conversion (wt %) 60.00 60.00 60.00 Yield of each ingredient (wt %) H₂0.14 0.14 0.15 C1-2 0.78 0.77 0.79 LPG 12.33 12.32 12.29 GASO 44.8944.96 44.90 LCO 29.81 29.92 29.87 HCO+ 10.21 10.13 10.28 COKE 1.84 1.761.72 RON 89.43 89.41 89.38 Selectivity (wt %): Metal provided amount:Ni/V = 3000/6000 (ppm) Conversion (wt %) 60.00 60.00 60.00 Yield of eachingredient (wt %) H₂ 0.29 0.30 0.31 C1-2 0.90 0.91 0.92 LPG 12.58 12.6912.49 GASO 43.66 43.87 43.91 LCO 28.09 27.97 27.92 HCO+ 12.30 12.2112.12 COKE 2.18 2.05 2.33 RON 89.75 89.67 89.52

[0203] 6. Bench-Scale Plant Activity Test Evaluation

[0204] A bench-scale plant comprising a circulating fluidized-bedreactor equipped with a reaction vessel and a catalyst regenerator wasused to conduct a test for evaluating the activity of catalysts.

[0205] Prior to the test, Catalysts (Base 2, C3, C8 and C9) weresubjected to the following circulating simulated equilibration.

[0206] As a feedstock oil was used the desulfurized vacuum distillationgas oil shown in Table 6. The test conditions used are as follows.

[0207] The test was conducted under conditions of a catalyst/hydrocarbonoil (weight ratio) of each of 6, 8, 10 and 12, and the results werecompared to evaluate the activity.

[0208] Reaction temperature: 500° C.

[0209] Catalyst/hydrocarbon oil weight ratio: 6, 8, 10, 12

[0210] Catalyst circulation amount: 60 g/min

[0211] Circulating Simulated Equilibration:

[0212] The method and apparatus described in JP-A-11-179192 (JapanesePatent Application No. 352940/1997) were used. A fresh catalyst or amixed catalyst composed of a fresh catalyst and a metal-providedcatalyst was heated to 775° C. and burned/steam-treated in an atmosphereof 50% air and 50% steam (heating/burning/stream treatment step).Thereafter, the mixed catalyst was cooled to room temperature, and ametal solution was atomized with nitrogen gas and adhered to thecatalyst. The catalyst was dried at 250° C. and the solvent vapor wasseparated with stripping with nitrogen gas (stripping step). Theoperation was repeated for 6 hours per day over 10 days.

[0213] Standard Conditions:

[0214] A treatment was conducted under the same conditions as in thecirculating simulated equilibration described above, except that theaverage provided-amounts of nickel and vanadium were regulated to 2,500and 5,000 ppm by weight, respectively, and the average steam treatmentperiod was changed to 20 hours.

[0215] Catalyst Life Doubling Conditions:

[0216] A treatment was conducted under the same conditions as thestandard conditions, except that the average provided amounts of nickeland vanadium were regulated to 5,000 and 10,000 ppm by weight,respectively, and the average steam treatment period was changed to 40hours.

[0217] In the treatment conducted under the standard conditions and thatconducted under the catalyst life doubling conditions, the metal sourcesused were naphthenic acid compounds diluted with toluene as in theMitchell method. TABLE 6 Hydrocarbon oils test d: vacuum distillationgas oil Sample 3 Density 15° C. g/cm³ 0.9094 Vacuum distillation IBP 330 5% ° C. 366 10% ° C. 382 20% ° C. 406 30% ° C. 424 40% ° C. 443 50% °C. 465 60% ° C. 488 70% ° C. 518 80% ° C. 553 End point ° C. 575 Totaldistillate amount % 85.0 Residue amount % 15.0 Loss % 0 Pour point ° C.20 Dynamic viscosity 50° C. mm²/S 56.22 Nitrogen content(chemiluminescence method) wt % 0.089 Sulfur content (X-ray method) wt %0.20 Refractive index 70 nD 1.487 Density 70° C. g/cm³ 0.8709 Molecularweight (calculated from viscosity) 498 Asphaltene (UOP) wt % 0.66 n-d-m(70° C.) % CA 16.6 % CN 16.0 % CP 67.4 Aniline point (U-tube method) °C. 95.1 Dynamic viscosity 75° C. mm²/S — Dynamic viscosity 100° C. mm²/S10.250 Basic nitrogen wt % 0.0181 Bromine number gBr₂/100 g 5.4 Hydrogencontent wt % 12.61 Carbon residue content wt % 2.23

[0218] TABLE 7 Catalyst name Base 2 C2 C8 C9 Metal deactivator name —MC-2 MC-7 MC-8 Conversion (wt %): Catalyst/oil 8 8 8 8 Average metalprovided amount: Ni/V (ppm) 2500/5000 60.80 67.43 67.52 67.21 5000/1000040.10 66.50 65.82 65.56 Selectivity (wt %): Average metal providedamount: Ni/V = 2500/5000 (ppm) Average steam treatment period: 20 hrConversion (wt %) 60.00 60.00 60.00 60.00 Yield of each ingredient (wt%) H₂ 0.23 0.14 0.13 0.13 C1-2 0.89 0.87 0.88 0.87 LPG 10.93 10.95 10.8210.79 GASO 41.24 42.35 42.35 42.41 LCO 21.37 22.98 23.21 22.93 HCO+19.08 17.32 17.38 17.68 COKE 6.26 5.39 5.23 5.19 RON 88.80 88.79 88.7888.79 Selectivity (wt %): Average metal provided amount: Ni/V =5000/10000 (ppm) Average steam treatment period: 40 hr Conversion (wt %)60.00 60.00 60.00 60.00 Yield of each ingredient (wt %) H₂ 0.31 0.250.23 0.22 C1-2 0.73 1.00 0.91 0.92 LPG 17.70 11.34 10.90 11.12 GASO35.86 41.65 42.21 42.34 LCO 17.25 23.38 23.12 23.46 HCO+ 20.25 16.2616.62 16.12 COKE 7.90 6.12 6.01 5.82 RON 88.80 89.50 89.34 89.45

[0219] While the invention has been described in detail and withreference to specific embodiments thereof, it will be apparent to oneskilled in the art that various changes and modifications can be madetherein without departing from the spirit and scope thereof.

[0220] This application is based on Japanese patent application No.2000-257669, filed on Aug. 28, 2000 and Japanese patent application No.2001-246232, filed on Aug. 14, 2001, the contents thereof being herebyincorporated by reference.

[0221] Industrial Applicability

[0222] As described above, the catalyst of the present invention hasreduced selectivity to hydrogen and coke and can yield a gasoline and anLCO fraction in high yields without lowering the octane number. Inaddition, the catalyst can retain these performances on a high levelover long. The FCC catalyst can have a greatly improved metal endurancelife (at least 3 times the life of Standard Catalyst A). (When afeedstock oil containing metals in an amount at least 3 times largerthan the metal amount in current feedstock oils is treated, the catalystof the present invention can have the same performance as currentcatalysts, i.e., Standard Catalyst A.)

[0223] According to the method of the present invention using thecatalyst, a low-quality heavy hydrocarbon oil can be cracked by FCC atlow cost.

1. A catalyst for fluidized catalytic cracking of a heavy hydrocarbonoil, which comprises a compound of a bivalent metal or a compound ofbivalent and trivalent metals showing an XRD pattern of a carbonate ofthe bivalent metal.
 2. The catalyst for fluidized catalytic cracking ofa heavy hydrocarbon oil according to claim 1, wherein the compound of abivalent metal or the compound of bivalent and trivalent metals isdispersed in an inorganic oxide matrix.
 3. The catalyst for fluidizedcatalytic cracking of a heavy hydrocarbon oil according to claim 1,wherein the compound of a bivalent metal or the compound of bivalent andtrivalent metals is dispersed in an inorganic oxide matrix together witha crystalline aluminosilicate zeolite.
 4. The catalyst for fluidizedcatalytic cracking of a heavy hydrocarbon oil according to any one ofclaims 1 to 3, wherein the bivalent metal in the compound of a bivalentmetal or in the compound of bivalent and trivalent metals is at leastone selected from the group consisting of Mn²⁺, Ca²⁺, Sr²⁺, Ba²⁺ andSn²⁺, and the trivalent metal therein is at least one selected from thegroup consisting of Al³⁺ and Mn³⁺.
 5. A method of fluidized catalyticcracking of a heavy hydrocarbon oil, which comprises using (1) StandardCatalyst A obtained by evenly dispersing a crystalline aluminosilicatezeolite in an inorganic oxide matrix and at least one of Catalyst Baccording to claim 1, Catalyst C according to claim 2, and Catalyst Daccording to claim 3 in combination, (2) Catalyst D and at least one ofCatalyst B and Catalyst C in combination, or (3) Catalyst D alone.